Methylolated alloxan



United States Patent Office 3,105,075 Patented Sept. 24, 1963 3,105,075 METHYLOLATED ALLOXAN Bethlehem K. Andrews, Metairie, La, assignor to the United States of America as represented by the Secretary of Agriculture No Drawing. Original application Aug. 19, 1960, Ser.

No- 50,808. Divided and this application Oct. 19, 1961, Ser. No. 151,129

Claims. (Cl. Zed-251) (Granted under Title 35, US. Code (1952), see. 266) A nonexclusive, irrevocable, royalty-free license in the invention herein described, throughout the world for all purposes of the United States Government, with the power to grant sublicences for such purposes, is hereby granted to the Government of the United States of America.

This invention relates to the treatment of cellulosic textiles in order to make them resistant to creasing and wrinkling.

It is well known that textiles which resist the formation of wrinkles and creases during use have long been preferred by consumers. Items, of which crease, muss, and wrinkle resistance are desirable characteristics include clothing, bed spreads, sheets, pillow cases, drapery and upholstery material, slipcovers, and others. Of these, in clothing, which usually requires frequent ironings to maintain a smooth appearance, wrinkle resistance is most important.

Various compounds have been applied to textiles to impart crease and wringle resistance, the most widely used ones being cyclic ethyleneurea-formaldehyde resins, ureaformaldehyde resins, melamine-formaldehyde resins, epoxy ethers, and formaldehyde. These compounds impart varying degrees of wrinkle resistance to the textiles, depending on the amount and type of wrinkle resistance agent used, the catalyst used, and the method of curing employed. Such textiles are usually called minimum care or wash-and-wear fabrics.

It is also important that the Wrinkle resistant textiles be resistant to fiber damage and discoloration due to retention of chlorine upon hypochlorite bleaching. importance is the durability of wrinkle-resistance finishes to both home and the more vigorous commercial launderings. With many of the above creaseproofing agents there is a compromise between maximum crease-resist ance to give a durable finish, and the susceptibility of the finish to degradation by retention of chlorine. In the case of formaldehyde, one of the greatest drawbacks is the precise control of conditions required for curing.

It is the purpose of this invention to produce a wrinkle resistance finish which will impart to textiles maximum crease resistance but negligible chlorine retention and damage due to such retention. Another object of this invention is to produce a crease resistance finish stable under acidic or alkaline conditions, durable to laundering and bisulfite or perborate bleaching. The crease resistance finish can be applied to textiles using a wide range of treating conditions. This is commercially advantageous.

The crease resistance finish which is the subject of this invention involves the reaction product of formaldehyde (including sources such as paraformaldehydes) and the ureide. of mesooxalic acid (alloxan). The latter compound is represented by the formula:

The finishing agent can be prepared by reacting from 1 to 4 or more moles of formaldehyde with one mole of the ureide under acidic conditions (pH 2-6) ,in suflicient water to give a 33 /3 percent solution of the reaction product. At least two moles formaldehyde is required Of equal H to prepare the dimethylol compound, however less can be used to prepare a partially methylolated compound. The solution thus prepared is diluted to the padding concentration and padded onto a cellulosic textile immediate ly or up to times in excess of three months.

In accordance with the invention an aqueous solution prepared as described above, and containing from 1 to 20 percent of the reaction product containing 2 or more moles of formaldehyde in combination with 1 mole of the ureide, is padded onto the cloth by passing through efilcient squeeze rolls, for example, using two dips and two hips to give dry add-ons of 0.01 percent to 5 or more percent based on the weight of the dry cloth. About 0.5 percent to 3 percent by weight, of a catalyst, based on the total weight of the padding bath, is added to the padding bath to facilitate curing, and to produce a more durable finish. Catalysts which can be used to promote curing include mineral acids, various salts of strong acids, such as ammonium salts, alkanolamine salts, metallic salts of strong acids and weak bases, such as zinc nitrate and magnesium chloride.

The curing step, the reaction of the formaldehyde-ureide with the textile is carried out by the usual procedure. The padded textile is dried at an elevated temperature, for example, '6070 C. for 7 minutes, then further heated to effect the curing. Improved properties are obtained at 120160 C. from 0.5 to 5 minutes. Curing temperatures above 160 C. are not generally employed, as they have a degrative eticct on the fabric. The curing time is temperature dependent, and can vary over a wide range. Thus, improved properties can be obtained at 160 C. for 30 to 60 seconds. The curing step is best followed, by an after wash with a non-ionic detergent, and 1 to 2 percent sodium perborate to remove any excess unreacted crease resistance agent and catalyst, to remove any discoloration brought on by curing, and to improve the hand of the textile.

The process to which this invention relates can be used to treat any hydrophilic fibrous cellulosic textiles such as cotton, linen, ramie, jute, regenerated cellulose, and others.

The following examples are given as illustrations and are not by any means intended to limit the scope of this invention. All percentages given in the examples are percentages by weight of the total solution. The fabrics were tested by the following methods: crease recovery angle, Monsanto method, American Society for Testing Materials (ASTM), Standards for Textile Materials D1295- 53T; tearing strength, Elmendorf Method AST M designation D1424-56T; damage caused by retained chlorine (scorch test) American Association of Textile Chemists and Colorists tentative test method 69-1952; wash-andwear (appearance) AATCC tentative test method 88- 1958. Two types of laundering were used to test the durability of the finish: ten home-type launderings were performed in an agitator-type home automatic Washer with a household detergent, 0.02% available chlorine in hot water, and followed by drying in a tumble dryer. The other laundering procedure was the more vigorous one described in AATCC test method 1453. To test acid durability the samples were allowed to stand for 30 minutes at C. in a stripping solution (50 times the sample weight) containing 5% urea and 1.5% phosphoric acid, rinsed in water, and dried in a tumble dryer.

EXAMPLE 1 A 33 /s% water solution of alloxan was prepared in the following manner: alloxan was dissolved in 2.8 times 'its weight in water and sufiicient 36.3% formaldehyde room temperature. After this time the 33 /3 solution was diluted with sufficient water to give a 7% sol-ids concentration, and /s% :by weight of hydrated magnesium chloride (MgCl -6H O) was added 'as catalyst. The

treating solution was padded onto a sample of -80 x 80 cotton print cloth to give a 7080% wet pickup. The wet fabric was dried at original dimensions for seven minutes at 60 C., and then cured at original dimensions for 3 minutes at l60 C. The curing step was followed by an after wash in warm water with a nonionic detergent, and 0.2% sodium perborate added, and then tumble drying. The finished fabric possessed a crease recovery angle of 275 (warp-ifill)'while an untreated, afterwashed sample had a crease recovery angle of only 187 (warp-i-fill).

EXAMPLE 2 A sample treated as described in Example 1 was sub- .jected to the urea-phosphoric acid stripping procedure.

The crease recovery angle of the fabric after stripping was 133 (warp), when compared with that of the original treated fabric 139 (warp) shows that severe acidic conditions do not remove the finish from the fabric. crease recovery angle of the untreated fabric is 95 n The 'To determine the effect of curing conditions on the physical properties of the finished fabric, a series of samples, treated with a solution containing 7% alloxan- ZOH O and 1.5% MgC1 -6H O, prepared as described in Example 1, were dried for 7 minutes at C., and cured as listed in Table II. After curing the samples were given an after Wash and tumble-dried as described in Example 1.

Table 11 Physical Properties Curing Curing Time (min) Tem- Add- Crease Recovery Tearing Strength perature On Wash- Angle (deg) (gms) (deg. Percent Wear 5 0.) Rating W F W W F W and and F' EXAMPLE 5 EXAMPLE 3 For comparison purposes the following percent solutions of all'oxan -2CH O were prepared and applied to 80 x 80 cotton print cloth with 1.5% MgCl -6H O as catalyst, and processed :as described in Example 1.

(A) A 33 /3 solution of the finishing agent prepared as in Example 1, was diluted with suflicient water to give a 1% solids concentration.

(B) A 33 /3 solution of the finishing agent, prepared as described in Example 1, was diluted with suflicient water to give a 5 solids concentration.

(C) A 33 /3 solution of the finishing agent, prepared as described in Example 1, was diluted with sufiicient water to give a 7 .5 solids concentration.

(D) A 33% solution of the finishing agent, prepared as described in Example .1, was diluted with suflicient water to give a 10% solids concentration.

-(E) A 33 /3 solution :of the finishing agent, prepared as described in Example 1, was diluted with suflicient water to give a 15% solids concentration.

(F) A 33 /3 solution of the finishing agent, prepared as described in Example 1, was diluted with suffioient water to give a 20% solids concentration.

Properties of the treated fabrics are given in Table I.

Solutions, 33 /s% of the finishing agent, prepared as described in Example 1 were adjusted with dilute NaOH to pH 4, pH 5, pH 6 before diluting to 7% padding concentration and addition of 1.5 MgCl -6H O and pad ding onto 80 x 80 cotton print cloth. The physical properties of the finishes obtained from these solutions were compared with those obtained from a alloxan-2CH O solution diluted without adjusting the'pH.

As can be seen from Table 111, an acceptable finish may be obtained when the pH of the finishing solution is high as 6.

EXAMPLE 6 by retained chlorine after 5 AATCC-14-53 washes than is the DMEU finish. After 10 home launderings the alloXan-2CH O finish is equal to the DMEU finish in resistance to damage by retained chlorine.

EXAMPLE 7 The -alloxan-2CI-I O in 3 3 /a% solution, prepared as described in Example 1 has a shelf life of more than one month. Fabric treated with a 7% solution of the stored finishing agent had a crease recovery angle of 133 (Warp). Fabric treated with a 7% solution, prepared from a 33% solution allowed to stand overnight before padding had a crease recovery angle of 139 p)- This application is a division of Serial No. 50,808, filed August 19, 1960, now US. 3,072,456.

Table I V Original After 5 AATCC 14-53 Washes Brk. Str Brk. Str. Crease Tearing Ret. After Crease Tearing Ret. After Ree. Strength AATCC Ree. Strength AATOO Finishing Agent Used Angle (Gms.) 69-1952 Angle (Gms) 69-1952 (Deg) Wand F Scorch (Deg) Wand F Scorch Wand F Test Per Wand F Test Percent Orig. cent Orig.

Untreated Fabric"--- 187 1, 907 91. a 172 1, 707 106. 4 7% DMA 275 514 82.0 265 507 102.8 7%% DMEU 300 787 94. s 277 887 46. 4

Table V I claim:

1. A compound having the structure:

After 10 Home Launderings With 0.02% 0=CNR Available Chlorine i 0:? I =0 Finishing Agent Used 0 R T m Bragg. Rat.

E2 535, 5 AATGrGQL wherein R is a member of the group consisting of H- (Deg.) Gms.) 1952 Scorch d CH 01-1 W dF W a F t, Fe 1: 2

an an Tes On'gf 40 2. The compound of claim 1 wherem R 1s H.

3. The compound of claim 1 wherein R is CH OH. Untreated fabric 172 1,233 102.0 4. A method for producing a textile-treating composigz'g gfi- 453 tion comprising reacting one mole of alloxan with about 0 from 1 to 4 moles of formaldehyde at a pH of about Tables IV and V show that the alloxan-2CH O finish is durable through both the home launderings and the more vigorous AATCC-1453 washes. The alloxan-2CH O finish is far superior in resistance to damage 5. The process of claim 4 wherein about from 2 to 4 moles of formaldehyde are reacted with one mole of alloxan.

No references cited. 

1. A COMPOUND HAVING THE STRUCTURE: 